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Synthesis, structure, spectral properties and theoretical studies of two half-sandwich titanium-complexes with adamantoxy ligands
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SYSNO ASEP 0474121 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Synthesis, structure, spectral properties and theoretical studies of two half-sandwich titanium-complexes with adamantoxy ligands Author(s) Varga, Vojtěch (UFCH-W) RID
Mach, Karel (UFCH-W) ORCID, RID
Pinkas, Jiří (UFCH-W) RID, ORCID
Kubišta, Jiří (UFCH-W) RID, ORCID
Szarka, K. (SK)
Gyepes, R. (SK)Source Title Journal of Molecular Structure. - : Elsevier - ISSN 0022-2860
Roč. 1142, AUG 2017 (2017), s. 248-254Number of pages 7 s. Language eng - English Country NL - Netherlands Keywords half-sandwich complex ; ionic complex ; solid-state structure Subject RIV CF - Physical ; Theoretical Chemistry OECD category Inorganic and nuclear chemistry R&D Projects GAP207/12/2368 GA ČR - Czech Science Foundation (CSF) GA14-08531S GA ČR - Czech Science Foundation (CSF) Institutional support UFCH-W - RVO:61388955 UT WOS 000402357000031 EID SCOPUS 85018513235 DOI 10.1016/j.molstruc.2017.04.072 Annotation Two novel half-sandwich Ti complexes, both incorporating two adamantoxy (OAd) ligands coordinated to their central atoms were synthesized. The complexes were characterized by H-1, C-13, F-19 NMR, El-MS and IR spectroscopy and by single-crystal X-ray diffraction. In both complexes, the coordination environment is pseudo-tetrahedral and is assembled of two O-coordinated adamantoxy and one eta(5)-coordinated permethylcyclopentadienyl ligand. The fourth ligand in complex 1 is a methyl group coordinated through a regular sigma-bond, whereas in complex 2 the same.coordination site is occupied by the methyl group of the balancing (C6F5)(3)BMe- anion. DFT computations complemented with NBO analyses of 2 have unveiled, that in addition to the electrostatic interactions occurring between the half-sandwich titanocene moiety and the anionic ligand, delocalization of one methyl C-H bond into the available acceptor orbital on the central atom takes place. AIM analyses of 2 have revealed the presence of a Bond Critical Point between the metal atom and the anionic methyl group. These results prove foundation for the description of 2 as a zwitterionic complex coupled with a concurrent Ti...C-H agostic interaction in its molecule. The comparison of 2 with its analogous complex equipped with two Ot-Bu ligands instead of both OAd has suggested only a minor change in the extent of the agostic interaction, despite significant geometric differences between the two complexes. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2018
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